The present invention relates to a catalyst component for the polymerization of olefins, a polymerization catalyst containing the component and a process for the polymerization of olefins by using the catalyst, and more particularly, to a catalyst component for the polymerization of olefins which is stable to air, moisture and so on and not corrosive to metal, a polymerization catalyst containing said component, having a high polymerization activity and being capable of producing olefin polymers, and a process for the polymerization of olefins.
Recently, as a catalyst which can homopolymerize ethylene or copolymerize ethylene and xcex1-olefin with a high polymerization activity, there is proposed a new catalyst for the polymerization of olefins comprising a transition metal compound such as metallocene compound of zirconium and an organic aluminum oxy compound. As a process for the homo-or copolymerization of ethylene by using such catalyst, there has been proposed, for example, in Japanese Patent Application Laid-open Nos. Sho 58(1983)-19309, Sho 60(1985)-35007, etc.
In such a prior art, it has been disclosed that as a transition metal compound component, a metallocene compound is available, which has an alkadienyl radical such as a cyclopentadienyl radical, etc, as a ligand for the transition metal, and further an alkyl radical, a halogen atom, etc.
However, the metallocene compound in such prior arts may show a high polymerization activity as a compound having a halogen atom bound directly to the transition metal atom, but need a treatment with alcohol or water after the polymerization depending on the kind of olefins and the process for the polymerization, so that hydrogen halide may be formed disadvantageously which may occur rusts and corrosions in equipments. Further, a metallocene compound having an alkyl radical bound directly to the metal atom has high polymerization activity relatively and does not form undesirable hydrogen halide, but there are some disadvantages that it is extremely unstable to a little air or moisture, is apt to lower the catalyst activity remarkably by deterioration in the operation or to deteriorate with time in storage, as a result, a special care and equipment to the handling and storage of catalyst component are required. Thus, for example, as seen in Japanese Patent Application Laid-open No. Sho 62(1987)-230802, there has been proposed a process in which the halogen atom or alkyl radical bound to the metal atom is converted to an alkoxy or phenoxy radical to eliminate the formation of hydrogen halide and improve the stability of the metallocene compound. In this case, however, disadvantageously the activity as catalyst for the polymerization of olefins is in general lowered.
Accordingly, it has been strongly desired to develop as a metallocene compound, a transition metal compound, which satisfies at the same time three requirements that it does not contain a halogen atom directly bound to the metal atom, as a result, it does not generate undesirable hydrogen halide, that it is stable to air and moisture so that it may be dealt with easily and has a high storage stability and that it has a high activity on using as a catalyst for the polymerization of olefins. And also it has been strongly desired to provide a process for the polymerization of olefins therewith.
After studying earnestly in view of the present status as mentioned above, it has been found that a metallocene compound may eliminate the disadvantages as mentioned above which has a radical comprising a cyclopentadienyl skeleton coordinated to the transition metal and in which an aromatic ring substituted with a special substituent is bound through an oxygen or a sulphur to the transition metal, and it shows an excellent activity on using it as a catalyst for the polymerization of olefins resulting in the accomplishment of the present invention.
Accordingly, the present invention relates at first to a catalyst component for the polymerization of olefins which comprises a transition metal compound represented by the general formula [1] or [2]:
(Ra Cp)m(Rxe2x80x2b Cp)nM(xe2x80x94Xxe2x80x94ARxe2x80x94Yc)4xe2x88x92(m+n)xe2x80x83xe2x80x83[1]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and Rxe2x80x2 represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, AR represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, a and b each is an integer of 0 to 5, m and n each is an integer of 0 to 3 and that m+n is an integer of 1 to 3, and c is an integer of 1 to 5, proviso Y does not present a hydrogen atom when AR is a benzene ring;
Rxe2x80x3(Rd Cp)(Rxe2x80x2e Cp)M(xe2x80x94Xxe2x80x94ARxe2x80x94Yc)2xe2x80x83xe2x80x83[2]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and Rxe2x80x2 represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, Rxe2x80x3 represents a divalent radical which links (Rd Cp) and (Rxe2x80x2e Cp) and is selected from an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, AR represents an aromatic radical, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, d and e each represents an integer of 0 to 4, and c is an integer of 1 to 5, proviso that Y is not a hydrogen atom when AR is a benzene ring.
Secondly, the present invention relates to a catalyst for the polymerization of olefins comprising [A] a transition metal compound represented by the above-mentioned general formula [1] or [2], [B] an organic aluminum oxy compound or a cation generator and occasionally [C] an organic aluminum compound, and thirdly to a process for the polymerization of olefins characterized by polymerizing or copolymerizing olefins in the presence of said catalyst for the polymerization of olefins.
The metallocene compound as a catalyst component for the polymerization of olefins has as mentioned-above in general a halogen atom or an alkyl radical as the groupings to bond the transition metal and the polymerization activity thereof is remarkably lowered when all groupings are converted to a phenoxy or thiophenoxy radical. However, the present inventors have found unexpected function in which in case a specified substutient is introduced to an aromatic ring like a phenoxy radical or thiophenoxy radical or the like, a higher polymerization activity is realized without the reduction of activity rather than the metallocene compound to which a halogen atom or an alkyl radical is bound.
The present invention will be illustrated in detail hereinafter, in which the term xe2x80x9cpolymerizationxe2x80x9d means the homopolymerization and copolymerization.
The metallocene catalyst component according to the present invention is a transition metal compound represented by any one of the following two general formulae:
(Ra Cp)m(Rxe2x80x2b Cp)nM(xe2x80x94Xxe2x80x94ARxe2x80x94Yc)4xe2x88x92(m+n)xe2x80x83xe2x80x83[1]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and Rxe2x80x2 represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, AR represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing radical, a and b each is an integer of 0 to 5, m and n each is an integer of 0 to 3 and m+n is an integer of 1 to 3, and c is an integer of 1-5, proviso that Y is not a hydrogen atom when AR is a benzene ring;
Rxe2x80x3(Rd Cp)(Rxe2x80x2e Cp)M(xe2x80x94Xxe2x80x94ARxe2x80x94Yc)2xe2x80x83xe2x80x83[2]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and Rxe2x80x2 represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, Rxe2x80x3 represents a divalent radical which links (Rd Cp) and (Rxe2x80x2e Cp) and is selected from an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl, or an alkylimino radical, X represents an oxygen or a sulphur atom, AR represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, d and e each is an integer of 0 to 4, and c is an integer of 1 to 5 proviso that Y is not a hydrogen atom when AR is a benzen ring;
In the general formulae [1] and [2], the ligand Cp is not critical but may be a grouping having the cyclopentadienyl skeleton and include not only a cyclopentadienyl radical but the cyclopentadienyl radicals in which two vicinal carbon atoms in the cyclopentadienyl ring bond to other carbon atoms to form a 4- or 5- or 6-membered ring. As the cyclopentadienyl radicals in which two vicinal carbon atoms in the cyclopentadienyl ring bond to other carbon atoms to form a 4- or 5- or 6-membered ring, there are mentioned, for example, an indenyl, tetrahydroindenyl, fluorenyl radical, etc.
In the general formulae [1] and [2], R and Rxe2x80x2 each is preferably, a hydrogen, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical having 2-20 carbon atoms, an aryl radical having 6 to 20 carbon atoms, an alkylaryl radical having 7 to 20 carbon atoms, an arylalkyl radical having 7 to 20 carbon atoms or an alkylsilyl radical having 3 to 20 carbon atoms.
In the general formula [1], as the grouping (Ra Cp) and (Rxe2x80x2b Cp) having the cyclopentadienyl skeleton, for example, cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, isobutylcyclopentadienyl, tert-butylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,3-trimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, trimethylsilylcyclopentadienyl, trimethylsilyltetramethylcyclopentadienyl, (phenyldimethylsilyl)cyclopentadienyl, triphenylsilylcyclopentadienyl, 1,3-di(trimethylsilyl)cyclopentadienyl, cyclohexylcyclopentadienyl, allylcyclopentadienyl, benzylcyclopentadienyl, phenylcyclopentadienyl, tolylcyclopentadienyl, indenyl, 1-methylindenyl, 2-methylindenyl, 2,4-dimethylindenyl, 4,7-dimethoxyindenyl, 4,7-dichloroindenyl, 5,6-dimethylindenyl, 2-methyl-4-ethyl-indenyl, 2-methyl-4,6-diisopropyl-indenyl, naphthylindenyl, 4,5,6,7-tetrahydroindenyl, 2-methyl-tetrahydroindenyl, fluorenyl, 2,7-di-tert-butylfluorenyl.
In the general formula [2], Rxe2x80x3 represents a divalent radical having 1 to 20 carbon atoms, which links (Rd Cp) and (Rxe2x80x2e Cp), and there are mentioned concretely alkylene, such as methylene, ethylene; alkylidene, such as ethylidene, propylidene, isopropylidene; arylalkylidene, such as phenylmethylidene, diphenylmethylidene; silylene, such as dimethylsilylene, diethylsilylene, dipropylsilylene, diisopropylsilylene, methylethylsilylene, methylisopropylsilylene, methyltert-butylsilylene, methylphenylsilylene, diphenylsilylene; germylene, such as dimethylgermylene, diethylgermylene, dipropylgermylene, diisopropylgermylene, diphenylgermylene, methylethylgermylene, methylisopropylgermylene, methyltert-butylgermylene, methylphenylgermylene, diphenylgermylene; alkylphophinediyl, such as methylphosphinediyl; alkylimino, such as methylimino; alkylboranediyl, such as methylborandiyl.
And, as the grouping Rxe2x80x3(Rd Cp) and (Rxe2x80x2e Cp) having the cyclopentadienyl skeleton in the general formula [2], there are mentioned, for example, ethylenebisindenyl, diphenylmethylenebisindenyl, dimethylsilylenebisindenyl, isopropylidenebisindenyl, dimethylsilylenebistetrahydroindenyl, isopropylidenecyclopentadienyl-1-fluorenyl, diphenylmethylencyclopentadienyl-1-fluorenyl, dimethylsilylenecyclopentadienyl-1-fluorenyl, dimethylsilylenbis(2,3,5-trimethylcyclopentadienyl), dimethylsilylenebis(2,4-dimethylcyclopentadienyl), dimethylsilylenebis(3-methylcyclopentadienyl), isopropylidenecyclopentadienyl-methylcyclopentadienyl, isopropylidenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl, diphenylmethylenecyclopentadienyl-methylcyclopentadienyl, diphenylmethylenecyclopentadienyl-2,4-dimethylcyclopentadienyl, diphenylmethylenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl, dimethylsilylencyclopentadienyl-methylcyclopentadienyl, dimethylsilylenecyclopentadienyl-2,4-dimethylcyclopentadienyl, dimethylsilylenecyclopentadienyl-2,3,5-trimethylcyclopentadienyl, isopropylidene-2,4-dimethylcycropentadienyl-1-fluorenyl, diphenylmethylene-2,4-dimethylcyclopentadienyl-1-fluorenyl, dimethylsilylene-2,4-dimethylcyclopentadienyl-1-fluorenyl, cyclohexylidenecyclopentadienyl-1-fluorenyl, dimethylgermylenebis-1-indenyl.
In the general formulae [1] and [2], Ph represents an aromatic radical, such as, for example, a benzene, naphthalene, anthrathene, indenyl, and phenanthrene ring.
Further, in the general formulae [1] and [2], the substituent Y is a radical which is selected from the group of a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical. And more concretely, it is a hydrocarbon radical such as an alkyl having 1-10 carbon atoms, an aryl having 6-10 carbon atoms, an alkenyl having 2-10 carbon atoms, an alkynyl having 2-10 carbon atoms, an arylalkyl having 7-20 carbon atoms, an arylalkenyl having 8-20 carbon atoms and an alkylaryl having 7-20 carbon atoms, or a silyl radical such as an alkylsilyl, an arylsilyl and the like, wherein the alkyl radical may include various kind of geometric isomers including cycloalkyl, proviso that as mentioned above a hydrogen atom is excluded when Ph is a benzene ring.
When the substituent Y is a hydrocarbon atom, there are mentioned an alkyl radical having 1-10 carbon atoms such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, cyclooctyl, norbornyl; an aryl radical having 6-10 carbon atoms such as, for example, phenyl, naphthyl; an alkenyl radical having 2-10 carbon atoms such as, for example, vinyl, propenyl; an alkynyl radical having 2-10 carbon atoms such as, for example, ethynyl, propynyl; an arylalkyl radical having 7-20 carbon atoms such as, for example, benzyl, phenethyl; an arylalkenyl radical having 8-20 carbon atoms such as, for example, stylyl, cinnamyl; and an alkylaryl radical having 7-20 carbon atoms such as, for example, tolyl, xylyl, mesyl, respectively.
When the substituent Y is an alkylsilyl radical, there are mentioned concretely, for example, trimethylsilyl and triethylsilyl radical, and when the substituent Y is an arylsilyl radical, there are mentioned a diphenylmethylsilyl and triphenylsilyl radical.
When the substutient Y is a halogen atom, there are mentioned concretely, for example, a fluorine, chlorine, bromine, iodine atom, and when the substutient Y is a halogenated hydrocarbon radical, there are mentioned concretely, for example, chloromethyl, fluoromethyl, bromomethyl, iodomethyl, dichloromethyl, difluoromethyl, dibromomethyl, diiodomethyl, trichloromethyl, trifluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, chlorophenyl, fluorophenyl, bromophenyl, iodophenyl, perfluorophenyl, chlorotetrafluorophenyl radical.
When the substutient Y is a nitrogen-containing organic radical, there are mentioned concretely, for example, a cyano, nitro, nitroso, isocyanide, cyanate, isocyanate, N-methylamino, anilino, N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diphenylamino, formamide, acetamide, N-methylacetamide, N-phenylacetamide radical.
When the substutient Y is an oxygen-containing organic radical, there are mentioned concretely, for example, a methoxy, ethoxy, propoxy, butoxy, phenoxy, formyl, acetyl, propyonyl, butylyl, valeryl, pyvaloyl, acyloyl, benzoyl, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy radical.
When the substutient Y is an sulphur-containing organic radical, there are mentioned concretely, for example, a methylthio, ethylthio, phenylthio, methylsulfinyl, ethylsulfinyl, benzenesulfiniyl, trisulfinyl, tolylsulfinyl, mesyl, tosyl radical.
The symbol of c in the general formulae [1] and [2] is a value which is selected from 1 to 5. In case c is 2 to 5 and the plural substutient Y are bonded together, the same and/or different substutient are available.
As the transition metal compounds according to the definition of the general formula [1] mentioned above, the following compounds may be exemplified:
dicyclopentadienylbis(2-fluorophenoxy)zirconium,
dicyclopentadienylbis(3-fluorophenoxy)zirconium,
dicyclopentadienylbis(4-fluorophenoxy)zirconium,
dicyclopentadienylbis(2-chlorophenoxy)zirconium,
dicyclopentadienylbis(3-chlorophenoxy)zirconium,
dicyclopentadienylbis(4-chlorophenoxy)zirconium,
dicyclopentadienylbis(2-bromophenoxy)zirconium,
dicyclopentadienylbis(3-bromophenoxy)zirconium,
dicyclopentadienylbis(4-bromophenoxy)zirconium,
dicyclopentadienylbis(2-iodophenoxy)zirconium,
dicyclopentadienylbis(3-iodophenoxy)zirconium,
dicyclopentadienylbis(4-iodophenoxy)zirconium,
dicyclopentadienylbis(2,3-difluorophenoxy)zirconium,
dicyclopentadienylbis(2,4-difluorophenoxy)zirconium,
dicyclopentadienylbis(2,5-difluorophenoxy)zirconium,
dicyclopentadienylbis(2,6-difluorophenoxy)zirconium,
dicyclopentadienylbis(3,4-difluorophenoxy)zirconium,
dicyclopentadienylbis(3,5-difluorophenoxy)zirconium,
dicyclopentadienylbis(2,3-dichlorophenoxy)zirconium,
dicyclopentadienylbis(2,4-dichlorophenoxy)zirconium,
dicyclopentadienylbis(2,5-dichlorophenoxy)zirconium,
dicyclopentadienylbis(2,6-dichlorophenoxy)zirconium,
dicyclopentadienylbis(3,4-dichlorophenoxy)zirconium,
dicyclopentadienylbis(3,5-dichlorophenoxy)zirconium,
dicyclopentadienylbis(2,3,4-trifluorophenoxy)zirconium,
dicyclopentadienylbis(2,3,5-trifluorophenoxy)zirconium,
dicyclopentadienylbis(2,3,6-trifluorophenoxy)zirconium,
dicyclopentadienylbis(2,4,5-trifluorophenoxy)zirconium,
dicyclopentadienylbis(2,4,6-trifluorophenoxy)zirconium,
dicyclopentadienylbis(3,4,5-trifluorophenoxy)zirconium,
dicyclopentadienylbis(2,3,5,6-tetrafluorophenoxy)zirconium,
dicyclopentadienylbis(pentafluorophenoxy)zirconium,
dicyclopentadienylbis(2-fluoromethylphenoxy)zirconium,
dicyclopentadienylbis(3-fluoromethylphenoxy)zirconium,
dicyclopentadienylbis(4-fluoromethylphenoxy)zirconium,
dicyclopentadienylbis(2-chloromethylphenoxy)zirconium,
dicyclopentadienylbis(3-chloromethylphenoxy)zirconium,
dicyclopentadienylbis(4-chloromethylphenoxy)zirconium,
dicyclopentadienylbis(2-trifluoromethylphenoxy)zirconium,
dicyclopentadienylbis(3-trifluoromethylphenoxy)zirconium,
dicyclopentadienylbis(4-trifluoromethylphenoxy)zirconium,
dicyclopentadienylbis(3,5-di-(trifluoromethyl)phenoxy)zirconium,
dicyclopentadienylbis(2-(2,2,2-trifluoroethyl)phenoxy)zirconium,
dicyclopentadienylbis(3-(2,2,2-trifluoroethyl)phenoxy)zirconium,
dicyclopentadienylbis(4-(2,2,2-trifluoroethyl)phenoxy)zirconium,
dicyclopentadienylbis(2-trichloromethylphenoxy)zirconium,
dicyclopentadienylbis(3-trichloromethylphenoxy)zirconium,
dicyclopentadienylbis(4-trichloromethylphenoxy)zirconium,
dicyclopentadienylbis(2-methylphenoxy)zirconium,
dicyclopentadienylbis(3-methylphenoxy)zirconium,
dicyclopentadienylbis(4-methylphenoxy)zirconium,
dicyclopentadienylbis(2,3-dimethylphenoxy)zirconium,
dicyclopentadienylbis(2,4-dimethylphenoxy)zirconium,
dicyclopentadienylbis(2,5-dimethylphenoxy)zirconium,
dicyclopentadienylbis(2,6-dimethylphenoxy)zirconium,
dicyclopentadienylbis(3,4-dimethylphenoxy)zirconium,
dicyclopentadienylbis(3,5-dimethylphenoxy)zirconium,
dicyclopentadienylbis(2,3,4-trimethylphenoxy)zirconium,
dicyclopentadienylbis(2,3,5-trimethylphenoxy)zirconium,
dicyclopentadienylbis(2,3,6-trimethylphenoxy)zirconium,
dicyclopentadienylbis(2,4,5-trimethylphenoxy)zirconium,
dicyclopentadienylbis(2,4,6-trimethylphenoxy)zirconium,
dicyclopentadienylbis(3,4,5-trimethylphenoxy)zirconium,
dicyclopentadienylbis(pentamethylphenoxy)zirconium,
dicyclopentadienylbis(2-methyl-4-fluorophenoxy)zirconium,
dicyclopentadienylbis(2-chloro-4-fluorophenoxy)zirconium,
dicyclopentadienylbis(2-chloro-4-trifluoromethylphenoxy)zirconium,
dicyclopentadienylbis(2-fluoro-4-trifluoromethylphenoxy)zirconium,
dicyclopentadienylbis(2-trifluoromethyl-4-florophenoxy)zirconium,
dicyclopentadienylbis(2-ethylphenoxy)zirconium,
dicyclopentadienylbis(3-ethylphenoxy)zirconium,
dicyclopentadienylbis(4-ethylphenoxy)zirconium,
dicyclopentadienylbis(2-isopropylphenoxy)zirconium,
dicyclopentadienylbis(3-isopropylphenoxy)zirconium,
dicyclopentadienylbis(4-isopropylphenoxy)zirconium,
dicyclopentadienylbis(2-tert-butylphenoxy)zirconium,
dicyclopentadienylbis(3-tert-butylphenoxy)zirconium,
dicyclopentadienylbis(4-tert-butylphenoxy)zirconium,
dicyclopentadienylbis(3,5-di-tert-butylphenoxy)zirconium,
dicyclopentadienylbis(2-trimethylsilylphenoxy)zirconium,
dicyclopentadienylbis(3-trimethylsilylphenoxy)zirconium,
dicyclopentadienylbis(4-trimethylsilylphenoxy)zirconium,
dicyclopentadienylbis(2-cyclohexylphenoxy)zirconium,
dicyclopentadienylbis(3-cyclohexylphenoxy)zirconium,
dicyclopentadienylbis(4-cyclohexylphenoxy)zirconium,
dicyclopentadienylbis(1-naphthyloxy)zirconium,
dicyclopentadienylbis(2-naphthyloxy)zirconium,
dicyclopentadienylbis(8-trifluoromethy-1-naphthyloxy)zirconium,
dicyclopentadienylbis(2,8-dimethyl-1-naphthyloxy)zirconium,
dicyclopentadienylbis(1-tert-butyl-2-naphthyloxy)zirconium,
dicyclopentadienylbis(8-bromo-2-naphthyloxy)zirconium,
dicyclopentadienylbis(2-phenylphenoxy)zirconium,
dicyclopentadienylbis(3-phenylphenoxy)zirconium,
dicyclopentadienylbis(4-phenylphenoxy)zirconium,
dicyclopentadienylbis(2-benzyphenoxy)zirconium,
dicyclopentadienylbis(3-benzylphenoxy)zirconium,
dicyclopentadienylbis(4-benzylphenoxy)zirconium,
dicyclopentadienylbis(2-tolylphenoxy)zirconium,
dicyclopentadienylbis(3-tolylphenoxy)zirconium,
dicyclopentadienylbis(4-tolylphenoxy)zirconium,
dicyclopentadienylbis(2-vinylphenoxy)zirconium,
dicyclopentadienylbis(3-vinylphenoxy)zirconium,
dicyclopentadienylbis(4-vinylphenoxy)zirconium,
dicyclopentadienylbis(2-(2-propenyl)phenoxy)zirconium,
dicyclopentadienylbis(3-(2-propenyl)phenoxy)zirconium,
dicyclopentadienylbis(4-(2-propenyl)phenoxy)zirconium,
dicyclopentadienylbis(2-methyl-6-(2-propenyl)phenoxy)zirconium,
dicyclopentadienylbis(2-ethynylphenoxy)zirconium,
dicyclopentadienylbis(3-ethynylphenoxy)zirconium,
dicyclopentadienylbis(4-ethynylphenoxy)zirconium,
dicyclopentadienylbis(2-methoxyphenoxy)zirconium,
dicyclopentadienylbis(3-methoxyphenoxy)zirconium,
dicyclopentadienylbis(4-methoxyphenoxy)zirconium,
dicyclopentadienylbis(2-tert-butoxyphenoxy)zirconium,
dicyclopentadienylbis(3-tert-butoxyphenoxy)zirconium,
dicyclopentadienylbis(4-tert-butoxyphenoxy)zirconium,
dicyclopentadienylbis(2-phenoxyphenoxy)zirconium,
dicyclopentadienylbis(3-phenoxyphenoxy)zirconium,
dicyclopentadienylbis(4-phenoxyphenoxy)zirconium,
dicyclopentadienylbis(2-formylphenoxy)zirconium,
dicyclopentadienylbis(3-formylphenoxy)zirconium,
dicyclopentadienylbis(4-formylphenoxy)zirconium,
dicyclopentadienylbis(2-acetylphenoxy)zirconium,
dicyclopentadienylbis(3-acetylphenoxy)zirconium,
dicyclopentadienylbis(4-acetylphenoxy)zirconium,
dicyclopentadienylbis(2-benzoylphenoxy)zirconium,
dicyclopentadienylbis(3-benzoylphenoxy)zirconium,
dicyclopentadienylbis(4-benzoylphenoxy)zirconium,
dicyclopentadienylbis(2-methoxycarbonylphenoxy)zirconium,
dicyclopentadienylbis(3-methoxycarbonylphenoxy)zirconium,
dicyclopentadienylbis(4-methoxycarbonylphenoxy)zirconium,
dicyclopentadienylbis(2-acetoxyphenoxy)zirconium,
dicyclopentadienylbis(3-acetoxyphenoxy)zirconium,
dicyclopentadienylbis(4-acetoxyphenoxy)zirconium,
dicyclopentadienylbis(2-cyanophenoxy)zirconium,
dicyclopentadienylbis(3-cyanophenoxy)zirconium,
dicyclopentadienylbis(4-cyanophenoxy)zirconium,
dicyclopentadienylbis(2-nitrophenoxy)zirconium,
dicyclopentadienylbis(3-nitrophenoxy)zirconium,
dicyclopentadienylbis(4-nitrophenoxy)zirconium,
dicyclopentadienylbis(2-anilinophenoxy)zirconium,
dicyclopentadienylbis(3-anilinophenoxy)zirconium,
dicyclopentadienylbis(4-anilinophenoxy)zirconium,
dicyclopentadienylbis(2-dimethylaminophenoxy)zirconium,
dicyclopentadienylbis(3-dimethylaminophenoxy)zirconium,
dicyclopentadienylbis(4-dimethylaminophenoxy)zirconium,
dicyclopentadienylbis(2-dimethylaminomethylphenoxy)zirconium,
dicyclopentadienylbis(3-dimethylaminomethylphenoxy)zirconium,
dicyclopentadienylbis(4-dimethylaminomethylphenoxy)zirconium,
dicyclopentadienylbis(2-formylaminophenoxy)zirconium,
dicyclopentadienylbis(3-formylaminophenoxy)zirconium,
dicyclopentadienylbis(4-formylaminophenoxy)zirconium,
dicyclopentadienylbis(2-acetylaminophenoxy)zirconium,
dicyclopentadienylbis(3-acetylaminophenoxy)zirconium,
dicyclopentadienylbis(4-acetylaminophenoxy)zirconium,
dicyclopentadienylbis(2-thiomethoxyphenoxy)zirconium,
dicyclopentadienylbis(3-thiomethoxyphenoxy)zirconium,
dicyclopentadienylbis(4-thiomethoxyphenoxy)zirconium,
dicyclopentadienylbis(2-thiophenoxyphenoxy)zirconium,
dicyclopentadienylbis(3-thiophenoxyphenoxy)zirconium,
dicyclopentadienylbis(4-thiophenoxyphenoxy)zirconium,
dicyclopentadienylbis(2-methylsulfinylphenoxy)zirconium,
dicyclopentadienylbis(3-methylsulfinylphenoxy)zirconium,
dicyclopentadienylbis(4-methylsulfinylphenoxy)zirconium,
dicyclopentadienylbis(2-mesylphenoxy)zirconium,
dicyclopentadienylbis(3-mesylphenoxy)zirconium,
dicyclopentadienylbis(4-mesylphenoxy)zirconium,
dicyclopentadienylbis(2-tosylphenoxy)zirconium,
dicyclopentadienylbis(3-tosylphenoxy)zirconium,
dicyclopentadienylbis(4-tosylphenoxy)zirconium,
dicyclopentadienylbis(2-trifluoromethanesulfonylphenoxy)zirconium,
dicyclopentadienylbis(3-trifluoromethanesulfonylphenoxy)zirconium,
dicyclopentadienylbis(4-trifluoromethanesulfonylphenoxy)zirconium,
dicyclopentadienylbis(2-methylthiophenoxy)zirconium,
dicyclopentadienylbis(3-methylthiophenoxy)zirconium,
dicyclopentadienylbis(4-methylthiophenoxy)zirconium,
dicyclopentadienylbis(2-tert-butylthiophenoxy)zirconium,
dicyclopentadienylbis(3-tert-butylthiophenoxy)zirconium,
dicyclopentadienylbis(4-tert-butylthiophenoxy)zirconium,
dicyclopentadienylbis(2-fluorothiophenoxy)zirconium,
dicyclopentadienylbis(3-fluorothiophenoxy)zirconium,
dicyclopentadienylbis(4-fluorothiophenoxy)zirconium,
dicyclopentadienylbis(2-chlorothiophenoxy)zirconium,
dicyclopentadienylbis(3-chlorothiophenoxy)zirconium,
dicyclopentadienylbis(4-chlorothiophenoxy)zirconium,
dicyclopentadienylbis(2-trifluoromethylthiophenoxy)zirconium,
dicyclopentadienylbis(3-trifluoromethylthiophenoxy)zirconium,
dicyclopentadienylbis(4-trifluoromethylthiophenoxy)zirconium,
dicyclopentadienylbis(2-methoxythiophenoxy)zirconium,
dicyclopentadienylbis(3-methoxythiophenoxy)zirconium,
dicyclopentadienylbis(4-methoxythiophenoxy)zirconium,
bis(methylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,
bis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,
bis(methylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,
bis(methylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,
bis(methylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
bis(methylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,
bis(methylcyclopentadienyl)bis(3-phenylphenoxy)zirconium,
bis(methylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadennyl)bis(3-ethylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(2,4-diethylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(2,5-diethylphenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(2-cyanophenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(3-cyanophenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(4-cyanophenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(2-bromophenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(3-bromophenoxy)zirconium,
bis(1,2-dimethylcyclopentadienyl)bis(4-bromophenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy) zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,
bis(1,3-dimethylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(2-isopropylphenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(3-isopropylphenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(4-isopropylphenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(2-nitrophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(3-nitrophenoxy)zirconium,
bis(1,2,3-trimethylcyclopentadienyl)bis(4-nitrophenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(2-methylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(3-methylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(4-methylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,
bis(1,2,4-trimethylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-methoxyphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-methoxyphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-methoxyphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-iodophenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-iodophenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-iodophenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(2-thiomethylphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(3-thiomethylphenoxy)zirconium,
bis(1,2,3,4-tetramethylcyclopentadienyl)bis(4-thiomethylphenoxy)zirconium,
bis(pentamethylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,
bis(pentamethylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,
bis(pentamethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
bis(ethylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,
bis(ethylcyclopentadienyl)bis(3-ethylphenoxy)zirconium,
bis(ethylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(2-acetylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(3-acetylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(4-acetylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(2-methylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(3-methylphenoxy)zirconium,
bis(isopropylcyclopentadienyl)bis(4-methylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(2-tert-butylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(3-tert-butylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(2-cyanophenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(3-cyanophenoxy)zirconium,
bis(n-butylcyclopentadienyl)bis(4-cyanophenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(2-fluorophenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(3-fluorophenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(2-ethylphenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(3-ethylphenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(4-ethylphenoxy)zirconium,
bis(tert-butylcyclopentadienyl)bis(2,4-dimethylphenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(2-chlorophenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(4-chlorophenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(1,3-di-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
bis(phenylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,
bis(phenylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,
bis(phenylcyclopentadienyl)bis(2,4-dichlorophenoxy)zirconium,
bis(trimethylcyclopentadienyl)bis(2-tert-butoxyphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(3-tert-butoxyphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(4-tert-butoxyphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(2-phenylphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(3-phenylphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(4-phenylphenoxy)zirconium,
bis(trimethylsilylcyclopentadienyl)bis(2,4-di-fluorophenoxy)zirconium,
bis(cyclohexylcyclopentadienyl)bis(2-iodophenoxy)zirconium,
bis(cyclohexylcyclopentadienyl)bis(3-iodophenoxy)zirconium,
bis(cyclohexylcyclopentadienyl)bis(4-iodophenoxy)zirconium,
bis(indenyl)bis(2-methylphenoxy)zirconium,
bis(indenyl)bis(3-methylphenoxy)zirconium,
bis(indenyl)bis(4-methylphenoxy)zirconium,
bis(1-methylindenyl)bis(2-fluorophenoxy)zirconium,
bis(1-methylindenyl)bis(3-fluorophenoxy)zirconium,
bis(1-methylindenyl)bis(4-fluorophenoxy)zirconium,
bis(2-methylindenyl)bis(2-bromophenoxy)zirconium,
bis(2-methylindenyl)bis(3-bromophenoxy)zirconium,
bis(2-methylindenyl)bis(4-bromophenoxy)zirconium,
bis(5,6-dimethylindenyl)bis(2-isopropylphenoxy)zirconium,
bis(5,6-dimethylindenyl)bis(3-isopropylphenoxy)zirconium,
bis(5,6-dimethylindenyl)bis(4-isopropylphenoxy)zirconium,
bis(5,6-dimethoxyindenyl)bis(2-cyanophenoxy)zirconium,
bis(5,6-dimethoxyindenyl)bis(3-cyanophenoxy)zirconium,
bis(5,6-dimethoxyindenyl)bis(4-cyanophenoxy)zirconium,
bis(fluorenyl)bis(2-chlorophenoxy)zirconium,
bis(fluorenyl)bis(3-chlorophenoxy)zirconium,
bis(fluorenyl)bis(4-chlorophenoxy)zirconium,
bis(4,5,6,7-tetrahydroindenyl)bis(2-tert-butylphenoxy)zirconium,
bis(4,5,6,7-tetrahydroindenyl)bis(3-tert-butylphenoxy)zirconium,
bis(4,5,6,7-tetrahydroindenyl)bis(4-tert-butylphenoxy)zirconium,
bis(2-methyltetrahydroindenyl)bis(2-nitrophenoxy)zirconium,
bis(2-methyltetrahydroindenyl)bis(3-nitrophenoxy)zirconium,
bis(2-methyltetrahydroindenyl)bis(4-nitrophenoxy)zirconium,
bis(2,7-di-tert-butylfluorenyl)bis(2-trifluoromethylphenoxy)zirconium,
bis(2,7-di-tert-butylfluorenyl)bis(3-trifluoromethylphenoxy)zirconium,
bis(2,7-di-tert-butylfluorenyl)bis(4-trifluoromethylphenoxy)zirconium, etc.
Further, in the present invention, the transition metal compounds may be used similarly, in which the zirconium atom in the zirconium compound of the general formula [1] as exemplified is substituted by a titanium or hafnium atom.
On the other hand, as the transition metal compounds represented by the general formula [2], the following compounds may be exemplified:
ethylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(indenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(indenyl)bis(4-chlorophenoxy)zirconium,
ethylenebis(indenyl)bis(2-fluorophenoxy)zirconium,
ethylenebis(3-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(3-methylindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(3-methylindenyl)bis(4-chlorophenoxy)zirconium,
ethylenebis(3-methylindenyl)bis(2-fluorophenoxy)zirconium,
ethylenebis(5,6-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(5,6-dimethylindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(5,6-dimethylindenyl)bis(4-chlorophenoxy)zirconium,
ethylenebis(5,6-dimethylindenyl)bis(2-fluorophenoxy)zirconium,
ethylenebis(4,7-dimethylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(4,7-dimethylindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(5,6-dimethoxylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(5,6-dimethoxylindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(5,6-dihydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(5,6-dihydroindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(5,6-dihydroindenyl)bis(4-chlorophenoxy)zirconium,
ethylenebis(5,6-dihydroindenyl)bis(2-fluorophenoxy)zirconium,
ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium,
ethylenebis(4,5,6,7-tetrahydroindenyl)bis(4-chlorophenoxy)zirconium,
ethylenebis(4,5,6,7-tetrahydroindenyl)bis(2-fluorophenoxy)zirconium,
methylenebis(cyclopentadienyl)bis(2-fluorophenoxy)zirconium,
methylenebis(cyclopentadienyl)bis(2-ethylphenoxy)zirconium,
methylenebis(methylcyclopentadienyl)bis(3-chlorophenoxy)zirconium,
methylenbis(1,3-dimethylcyclopentadienyl)bis(2-trifluoromethylphenoxy)zirconium,
methylenbis(n-butylcyclopentadienyl)bis(4-tert-butylphenoxy)zirconium,
ethylenbis(3-methylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenbis(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
ethylenbis(3-isopropylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenbis(3-isopropylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
ethylenbis(3-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
ethylenbis(3-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
isopropylidene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
isopropylidene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium,
isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
isopropylidene(methylcyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium,
isopropylidenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
isopropylidenebis(indenyl)bis(4-fluorophenoxy)zirconium,
isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium,
isopropylidene(cyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium,
isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-trifluoromethylphenoxy)zirconium,
isopropylidene(3-methylcyclopentadienyl)(fluorenyl)bis(4-fluorophenoxy)zirconium,
tetramethylethylidenebis(2-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
tetramethylethylidenebis(2-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-methylidenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-ethylidenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(2-ethylindenyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(2-methyl-5-isopropylindenyl)bis(4-fluorophenoxy)zirconium, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-tert-butylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(2-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-tert-butyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(2-isopropyl-4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(2,4,5-trimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(3,5-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-tert-butylcyclopentadienyl)(4-tert-butylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-methylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3,4-dimethylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-tert-butylcyclopentadienyl)(3-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-tert-butylcyclopentadienyl)(4-methylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,3,5-trimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(2,4-dimethylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-tert-butylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(3-methylcyclopentadienyl)(cyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylene(cyclopentadienyl)(indenyl)bis(4-fluorophenoxy)zirconium,
diphenylsilylene(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
diphenylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,
dibenzylsilylenebis(indenyl)bis(4-trifluoromethylphenoxy)zirconium,
dibenzylsilylenebis(indenyl)bis(4-fluorophenoxy)zirconium,
methylphenylsilylenebis(2-methylindenyl)bis(4-trifluoromethylphenoxy)zirconium,
methylphenylsilylenebis(2-methylindenyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(3,4-dimethylcyclopentadienyl)bis(4-fluorophenoxy)zirconium,
dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-trifluoromethylphenoxy)zirconium,
dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)bis(4-fluorophenoxy)zirconium.
The transition metal compounds, in which the zirconium atom of the zirconium compounds as mentioned above of the formula [2] is substituted by a titanium or hafnium atom, also may be used similarly.
The transition metal compounds according to the present invention may be synthesized by some known processes. The transition metal compound represented by the general formula [1] is synthesized, for example, by a process in which the IVA group transition metal compound represented by the general formula [3] is reacted at first with alkyl lithium to form the reactive intermediate compound of the general formula [4]. Then, the intermediate compound is reacted with an aromatic hydroxy or thiol compound having a specified substituent represented by the general formula [5] to form a final transition metal compound according to the reaction equation [6]:
(Ra Cp)m(Rxe2x80x2b Cp)nMZ4xe2x88x92(m+n)xe2x80x83xe2x80x83[3]
wherein Ra Cp and Rxe2x80x2b Cp each represents a grouping having the cyclopentadienyl skeleton, M is titanium, zirconium or hafnium, Z is a halogen atom, a and b each is an integer of 0-5, m and n each is an integer of 0-3, and m+n is an integer of 1-3;
(Ra Cp)m(Rxe2x80x2b Cp)nMQ4xe2x88x92(m+n)xe2x80x83xe2x80x83[4]
wherein (Ra Cp) and (Rxe2x80x2b Cp), M, a, b, m and n each has the same meaning in the general formula [3] and Q represents an alkyl radical;
(4xe2x88x92mxe2x88x92n)Hxe2x80x94Xxe2x80x94Arxe2x80x94YCxe2x80x83xe2x80x83[5]
wherein X represents an oxygen or sulphur atom, Ar represents an aromatic ring, Y represents a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, and c is an integer of 1-5;
(Ra CP)m (Rxe2x80x2b CP). MQ4xe2x88x92(m+n)Hxe2x80x94Xxe2x80x94Arxe2x80x94Ycxe2x86x92(Ra Cp)m (Rxe2x80x2b CP)n M(Xxe2x80x94Arxe2x80x94Y)4xe2x88x92(m+n)+(4xe2x88x92mxe2x88x92n)QHxe2x80x83xe2x80x83[6]
wherein Ra Cp and Rxe2x80x2b Cp, M, Q, X, Ar, Y, a, b, m, n and c each has the same meaning in the general formulae [4]-[5].
In the reaction equation [6], the reaction temperature is xe2x88x9278xc2x0 C. to 100xc2x0 C., preferably 0xc2x0 C. to 80xc2x0 C., and the reaction time is 0.1 to 50 hrs, preferably 0.5 to 30 hrs. As a solvent to be used in the reaction, there is used, for example, an aliphatic hydrocarbon such as hexane and decane; an aromatic hydrocarbon such as benzene, toluene or xylene; ethers such as tetrahydrofuran and diethylether; and a halogenated hydrocarbon such as chloroform and dichloromethane. These reaction solvents may be used generally in an amount within 10 to 500 times of the compound of the general formula [3] or [4].
The reaction of the equation [6] proceeds in general quantitatively so that the compound of the general formula [4] and [5] may be reacted each other in a stoichiometrically required amount. When the solvent is distilled off in vacuum from the reaction solution after the reaction, the final transition metal compound is obtained. Of course, after the solvent is distilled off in vacuum from the solution after the reaction of equation [6], the final compound may be further purified by a process such as recrystallization.
As other process for synthesizing the transition metal compound according to the present invention, there may be used aprocess in which the compound of the general formula [3] is reacted directly with an alkali metal salt of the compound of the general formula [5] and a process, which is described for example in Journal of Organometallic Chemistry 485 (1995) 153-160, i.e. a process in which the compound of the formula [3] is reacted directly with the compound of the formula [5] in the presence of base compound such as an amine.
On the other hand, the transition metal compound represented by the general formula [2] may be synthesized in the same manner as in the process for synthesizing the compound of the general formula [1].
The catalyst for the polymerization of olefins according to the present invention is characterized by using as co-catalyst an organic aluminum oxy compound or a cation generator and, if necessary, an organic aluminum compound in combination of said transition metal compound.
The organic aluminum oxy compound may be selected from the linear alkylaluminoxanes of the general formula [7] and the cyclic alkylaluminoxanes of the general formula [8]. 
Wherein R1 represents a hydrogen atom, a halogen atom or an alkyl radical having 1 to 10 carbon atoms and m is an integer of 2 to 40. 
Wherein R1 and m each has the same meaning in the general formula [7].
As to R1 in the general formulae [7] and [8], the halogen atom is a chlorine or bromine atom and the alkyl radical having 1-10 carbon atoms is methyl, ethyl, iso-butyl and the like. The compound of the formulae [7] and [8] may be contain different R1 radical therein. Preferably, the compound has above all methyl or methyl and other radicals. The number of repeating unit, m, is selected from within the range of 2-40, preferably 5-20.
Various known processes may be used for the synthesis of the alkylalminoxanes of the formulae [7] and [8]. For example, the compounds may be synthesized by a process in which a trialkyl aluminum is dissolved in a hydrocarbon solvent and hydrolyzed by adding gradually an equivalent amount of water to the trialkyl aluminum in the solution; a process in which a hydrate of copper sulfate or aluminum sulfate is suspended in a hydrocarbon solvent and a trialkyl aluminum in an amount of 1-3 times equivalent to the crystal water of said hydrate in the suspension is contacted to the hydrate to hydrolyze gradually the trialkylaluminum; or a process in which the adsorption water of undehydrated silica gel suspended in a hydrocarbon solvent is contacted to a trialkyl aluminum in an amount of 1 to 3 times equivalent to said adsorption water to hydrolyze gradually the trialkyl aluminum.
On the other hand, as the cation generator among the co-catalyst, there are mentioned those of the neutral and ion-pair type; those of neutral type include, for example, the organic boron compounds represented by the general formula [9]
BR23xe2x80x83xe2x80x83[9]
wherein R2 represents a hydrogen atom, a hydrocarbon radical having 1 to 20 carbon atoms or a halogen atom.
Preferably, the compounds of the general formula [9] are especially those, in which a hydrocarbon radical to be bonded to the boron atom. The three R2 radical may be same or different and except for hydrocarbon radicals, a part of three R2 may be substituted by a hydrogen or halogen atom.
Examples of R2 include an alkyl radical such as methyl, ethyl, n-propyl, iso-butyl and n-octyl; or an aryl radical such as phenyl and tolyl.
Concrete examples of the organic boron compounds of the formula [9] include triphenylborane, tris(pentafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(2,4,6-trifluorophenyl)borane, tris(2,3-difluorophenyl)borane, tris(2-fluorophenyl)borane, tris[3,5-bis(trifluoromethyl)phenyl]borane, tris[4-(trifluoromethyl)phenyl]borane, trimethylborane, triethylborane, tris(trifluoromethyl)borane, diphenylfluoroborane, bis(pentafluorophenyl)chloroborane. Of these, prefered ones are tris(pentafluorophenyl)borane and tris[3,5-bis(trifluoromethyl)phenyl]borane.
The ion pair type cation generators are compounds of the formula [10]
[On]+[BR34]xe2x88x92xe2x80x83xe2x80x83[10]
wherein [On]+ is a metal cation of group 1B, 2B, or 8, carbenium ion, silicenium ion, oxonium ion, sulfonium ion, ammonium ion or phosphonium ion, and R3 is a hydorocarbon radical having 1 to 20 carbon atoms, respectively.
Concrete examples of the cation generators of the formula [10] include salts of tetrakis(pentafluorophenyl)borate, such as ferrocenium tetrakis(pentafluorophenyl)borate, silver (I) tetrakis(pentafluorophenyl)borate, copper (I) tetrakis(pentafluorophenyl)borate, marcury (II) bis[tetrakis(pentafluorophenyl)]borate, palladium (II) bis[tetrakis(pentafluorophenyl)]borate, platinum (II) bis[tetrakis(pentafluorophenyl)]borate, diphenylhydorocarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tricyclohexylcarbenium tetrakis(pentafluorophenyl)borate, triphenylsilicenium tetrakis(pentafluorophenyl)borate, triethyloxonium tetrakis(pentafluorophenyl)borate, triethylsulfonium tetrakis(pentafluorophenyl)borate, diethylanilinium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tetra- n-butylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate.
In the practice of the present invention, the organic aluminum compound represented by the general formula [11] may be co-existed, if necessary, in order to stabilize the catalyst or in order to stabilize the organic aluminum oxy compound or cation generator as the above-mentioned co-catalyst and reduce the amount to be used.
R43Alxe2x80x83xe2x80x83[11]
wherein R4 represents a hydrogen atom, an alkyl radical having 1-10 carbon atoms or a halogen atom, proviso that all R4 radicals are not hydrogen or halogen atoms.
R4 as an alkyl radical having 1-10 carbon atoms is, for example, methyl, ethyl, iso-butyl or octyl radical and as a halogen atom is, for example, a chlorine or bromine atom. Further, the radical R4 of the compounds represented by the general formula [11] may be same or different.
As the compounds of the formula [11], there may be mentioned, for instance, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diisobutylaluminum hydride, diethtylaluminum chloride, ethylaluminum sesquichloride.
In the practice of the polymerization of olefines in the present invention, the catalyst for the polymerization may be prepared by adding the transition metal compound according to the present invention as catalyst component and an organic aluminum oxy compound or cation generator as a co-catalyst, and if necessary, an organic aluminum compound to an inert hydrocarbon solvent or an olefin medium to be polymerized. Then, the addition order of each component may be selected optionally, the transition metal compound and co-catalyst may be used after mixing and contacting them for a certain time before the polymerization previously, or each component may be also added respectively to the polymerization system.
The transition metal compound according to the present invention for the polymerization of olefins is used in general in a catalyst concentration within the range of 10xe2x88x928-10xe2x88x921 mol/liter, preferably 10xe2x88x927-10xe2x88x923 mol/liter. On the other hand, the organic aluminum oxy compound as co-catalyst is used in general within the range of 10-105, preferably 50 to 5xc3x97103 of the ratio of aluminum atom/transition metal atom. The cation generator as co-catalyst is used in general within the range of 0.5 to 10, preferably 1 to 5 of the mol ratio of cation generator/transition metal compound. The organic aluminum compound of the general formula (11) is used in general within the range of 1 to 105, preferably 10 to 104 of the ratio of aluminum atom/transition metal atom.
The polymerization according to the present invention can be carried out by means of every polymerization process such as the slurry, solution or gas-phase polymerization. In the slurry or gas-phase polymerization, either the catalyst component of the transition metal compound or the co-catalyst or both of them may be deposited on a support for use. Examples of support include, for example, an inorganic oxide support such as silica, alumina or silica-alumina; an inorganic support such as magnesium chloride; and an organic support such as polyethylene and polypropylene. The method for supporting on a support is not critical and any known method may be used. The catalyst supported on a support may be subjected to the so-called prepolymerization treatment, in which a relatively small amount of olefin is previously polymerized in the polymerization of olefines, where the amount of olefin polymer to be produced is preferably up to 0.05 to 500 g, preferably up to 0.1 to 100 g per g of the carried catalyst. A process in which either the catalyst component or the co-catalyst or both of them is supported on a support and used, or a process in which either the catalyst component or the co-catalyst or both of them is used after the prepolymerization, is a available especially for the slurry or gas-phase polymerization because the particle shape and bulk density of the polymer produced are improved and the like.
Olefins to be used in the process according to the present invention include not only xcex1-olefins but also those other than xcex1-olefins for example, linear diolefins, cyclic olefins, cyclic polyenes, aromatic vinyl compounds, or the like.
As alpha-olefins, those having 2 to 20 carbon atoms are particularly mentioned. For instance, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane, vinylcyclohexene, trimethylvinylsilane may be mentioned.
Linear diolefins are, particularly, those having 4 to 20 carbon atoms. For instance, non-conjugated dienes, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 1,7-octadiene, 7-methyl-1,6-octadiene and 1,9-decanediene, or conjugated dienes, such as butadiene, isoprene, chloroprene, 1,3-pentadiene and 1,3-hexadiene may be mentioned.
Cyclic olefins are, particularly, those having 4 to 40 carbon atoms. For instance, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-chloro-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxylnorbornene anhydrate, tetracyclododecene, 5-phenylnorbornene may be mentioned.
Cyclic polyenes are, particularly, those having 5 to 40 carbon atoms. For instance, cyclopentadiene, dicyclopentadiene, norbornadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, cyclooctatriene may be mentioned. As aromatic vinyl compounds, for instance, styrene, alpha-methylstyrene, divinylbenzene are usable.
These olefins may be homopolymerized and two or more than two olefins may be copolymerized.
In the present invention, an inert hydrocarbon solvent or the olefin itself to be polymerized may be used for carrying out the solution or slurry polymerization. As inert hydrocarbon solvents, there may be used, for example, an aliphatic hydrocarbon such as butane, isobutane, pentane, hexane, octane, an alicyclic hydrocarbon such as cyclopentane, methylcyclopentane or cyclohexane; an aromatic hydrocarbon such as benzene, toluene or xylene; and a petroleum fraction such as naphtha, kerosene or light oil.
The polymerization temperature in the practice of the polymerization of the present invention is in general within the range of xe2x88x9220 to 100xc2x0 C., preferably 20 to 90xc2x0 C. in the slurry polymerization, and in general within the range of 0 to 120xc2x0 C., preferably 20 to 100xc2x0 C. in the gas-phase polymerization; it is in general within the range of 0 to 300xc2x0 C., preferably 100 to 250xc2x0 C. in the solution polymerization. The polymerization pressure is not critical, but is used in general within the range from a atomospheric pressure to 100 kg/cm2.
The polymerization according to the present invention may be carried out in a batch, semi-continuous or continuous method and in two or more than two steps of different reaction condition. The molecular weight (weight average molecular weight) of olefin polymer obtained by using the catalyst according to the present invention is in general 1,000 to 10,000,000, especially 5,000 to 5,000,000. The molecular weight of olefin polymer obtained may be controlled by the presence of hydrogen in the polymerization reaction system or the change of polymerization temperature.